Process for producing cellulosic shaped articles, cellulosic shaped articles and the use thereof

ABSTRACT

The invention relates to a process for producing cellulosic shaped articles with stabilized inclusions in a microfine dispersion of nonpolar organic compounds and mixtures by a dry-wet extrusion process. The shaped articles produced in this way exhibit by comparison with unmodified cellulose fibers a substantially increased storage capacity for heat and/or nonpolar active substances. They are suitable in particular for use in textiles for clothing, industrial textiles, leisure, medicine and cosmetics. Potential functional effects imparted include the physical effect of heat storage and/or the uniform and finely meterable storage and release of nonpolar active substances and plant extracts from the interior of the fibers of the shaped articles. It is possible through a suitable choice of the nonpolar portion to produce by this process also fibers capable of absorbing liquid or gaseous nonpolar substances.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is being filed under Rule 1.371 as a National StageApplication of pending International Applicaton No. PCT/EP2008/009497filed Nov. 11, 2008, which claims priority to patent application GermanPatent Application No. 10 2007 054 702.3, filed Nov. 14, 2007. BothInternational Application Nos. PCT/EP2008/009497 and German PatentApplication No. 10 2007 054 702.3 are hereby incorporated by referenceherein in their entirety.

FIELD OF THE INVENTION

The invention relates to a process for producing cellulosic shapedarticles with inclusions of at least one nonpolar organic compound bythe dry-wet extrusion process, to a cellulosic shaped article and to theuse thereof.

BACKGROUND OF THE INVENTION

It is known that the heat storage capacity of textile fibers and shapedarticles can be increased if the shaping polymer is combined with anorganic phase change material which can exchange energy with thesurrounding area through melting/solidification transition,conformational transition or deorientation/crystallization. The extentof the energy exchange and the effective temperature range correlatewith the chemical structure, the change in physical enthalpy and theconcentration of the phase change material. It is primarily decisivethat the energy exchange effect in the fiber is retained as the resultof the molecular near-orientation of the phase change material in or onthe shaped article. The following solutions are known:

Firstly, phase change materials are encapsulated with an organic polymerlayer and then the capsules are incorporated into a polymer fiber orapplied to a fabric (e.g. EP 1 658 395=US 2006/0279017).Micro-encapsulated phase change materials are also used in the examplesaccording to WO 2005/017247 in the production of cellulose fibers havingthermoregulatory properties by the Lyocell process. It has provendisadvantageous here that the encapsulation of the phase change materialtakes place separately from the shaping, or from the processing.Inevitably, a compromise between available capsule batches as regardsmaterial and suitability for the shaping process is necessary. In thecase of dry-wet extrusion processes, requirements such as fineness andparticle size distribution, mechanical and chemical stability,suitability of the phase change material for the field of use,availability and cost, inter alia, are placed on microcapsules.

Furthermore, phase change materials can be incorporated into apolyolefin matrix or a polymer suspension. For example, the productionof melt-spun polyolefin fibers which comprise phase change materialshaving a melting point from 15 to 65° C. is known (U.S. Pat. No.5,885,475).

The direct incorporation of a phase change material (e.g. a polyethyleneglycol) into a hollow fiber is described in U.S. Pat. No. 4,908,238.Here, however, stabilization of the phase change material in the shapedarticle was dispensed with. From the point of view of the structure, itresembles a microsandwich construction. Simple sandwich structures aredisclosed e.g. in US 2003/124278.

According to one particular embodiment in WO 03/027365 (=EP 1 430 169),it should be possible to mix in the PCM during the production of acellulose fiber in raw form. However, here, no permanent bonding of thePCM to the matrix material (cellulose) can arise, and it is also notpossible to spin a fiber from a mixture of PCM and dissolved cellulose.

There is interest in releasing active ingredients from a woven or acellulose fiber. It is also known to anchor encapsulated,active-ingredient-containing material to the surface of fibers (WO01/73188) or to incorporate them therein (WO 2006/066291). Thepossibility of producing fragrances and active ingredients asmicrocapsules is described e.g. in EP 1 243 326. Again, as a result ofthe limited availability, the microcapsule has proven to bedisadvantageous for industrial application since the encapsulation takesplace separately from the shaping.

No approaches are known from the literature as to how the generation ofpermanent nonpolar organic micro-inclusions into a hydrophilicnetwork-forming polymer, such as cellulose, can be realized by addingthe raw materials (solvent, cellulose, nonpolar organic compounds andmixtures, thickeners and phase promoters) to the spinning solution andsubsequent shaping in one process. Hitherto, it has also not beendescribed that organic compounds which may be dissolved or suspended inthe nonpolar organic compounds and mixtures can be used as modifiers(change in the melting range of phase change materials by e.g. loweringthe melting point) or releaseable active ingredients if they were to beincorporated as permanent, nonpolar organic micro-inclusions into ahydrophilic network-forming polymer, such as cellulose.

Only the incorporation of nanoscale active ingredients in powder formand/or of carbon nanotubes was known (WO 2004/081267). Teaching withregard to the incorporation of lipophilic substances into a polarcellulose solution cannot be inferred therefrom.

Proceeding from prior art as described in WO 2006/066291, the object ofthe invention was accordingly to develop a direct process for producingcellulosic shaped articles with inclusions of nonpolar organic compoundsand mixtures utilizing the direct incorporation of these organic,nonpolar compounds and mixtures. If appropriate, these cellulosic shapedarticles with inclusions of nonpolar organic compounds should beequipped with further functional additives which are concentratedparticularly at or close to the surface of the inclusions.

Moreover, it is within the scope of the object to develop a process inwhich active ingredients can be dissolved and/or stored in cellulosicshaped articles and can be released to the surrounding area in acontrolled manner over a prolonged period.

SUMMARY OF ADVANTAGEOUS EMBODIMENTS OF THE INVENTION

According to the invention, this object is achieved in that

-   -   an emulsion with at least one nonpolar organic compound in a        solution of cellulose in a solvent is prepared and stabilized by        adding at least one hydrophobic viscosity-increasing agent,        and/or    -   nanoscale, sheet-like and/or elongated, hydro-phobicized        particles, for example sheet silicates, nanotubes or        nanofilaments, are added to the emulsion; these surround the        droplet-like inclusions of the nonpolar organic compound(s) and        form a suspension,        and    -   the cellulose is recrystallized, giving shaped articles with a        cellulose matrix in which the nonpolar organic compound(s)        is/are incorporated in disperse form.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a diagrammatic view off an exemplary inventive cellulosicfiber; and

FIG. 2 is a sectional view through an individual inclusion and itssurrounding area within the exemplary inventive cellulosic fiberaccording to FIG. 1.

DETAILED DESCRIPTION OF ADVANTAGEOUS EMBODIMENTS OF THE INVENTION

In the process, a cellulosic shaping and spinning solution, which can beprepared by dissolving cellulose in a suitable solvent, is admixed witha nonpolar organic material, the viscosity of the nonpolar material isincreased so that it can be emulsified in the cellulose solution, andthe dispersed phase of the nonpolar material is stabilized. Ifsheet-like and/or elongated nanoscale particles are added, such ashydrophobicized sheet minerals, e.g. sheet silicates and bentonites,which are exfoliated in the spinning mass, the dispersed phase issurrounded with a layer of these nanoparticles.

Instead of cellulose or in addition to it, any desired polysaccharidesin natural or synthetically produced form can be used and/or alsomixtures of polysaccharides. Examples are wood cellulose, starch, jute,flax, cotton linters, chitosan or mixtures thereof.

Suitable solvents are, for example, aqueous solutions of tertiary amineoxides, such as N-methylmorpholine N-oxide, and also ionic liquids,preferably ethylmethylimidazolium acetate. It has been found that otherionic liquids are also suitable as solvents for this process, forexample 1-butyl-3-methylimidazolium chloride (BMIMCI),1-ethyl-3-methylimidazolium chloride (EMIMCI),1-butyl-3-methylimidazolium acetate (BMIMAc) and1-ethyl-3-methylimidazolium acetate (BMIMAc), N,N-dimethylacetamidelithium chloride, 1-alkyl-3-methylimidazolium salts.

In the process according to the invention, the production and thespinning of a physical solution of the cellulose takes place withoutderivatization thereof by preparing an emulsion with at least onenonpolar organic compound in a solution of cellulose inN-methylmorpholine N-oxide or an ionic liquid and stabilizing it byadding hydrophobic viscosity-increasing agents (thickeners), and forminga suspension and recrystallizing the cellulose, giving shaped articleswith a cellulose matrix in which the nonpolar organic compound isincorporated in disperse form. If appropriate, nanoscale, sheet-likeand/or elongated, hydrophobicized particles can be added to theemulsion; these surround the incorporated droplets of the nonpolarorganic compound, which leads to further stabilization of the nonpolarmaterial.

When working with ionic liquids, it is of particular interest that theprocessing of suitable cellulose/salt solutions at temperatures below90° C. since the spinning dope, in contrast to cellulose/amine oxidesolutions, does not solidify and thus remains shapeable in a relativelywide temperature window from room temperature to 120° C. For example, itis thus also possible to process nonpolar materials with a significantvapor pressure at 90° C.

The nonpolar organic compound is preferably a hydrocarbon, a wax,beeswax, an oil, a fatty acid, a fatty acid ester, stearic anhydride, along-chain alcohol or any desired mixture thereof. It generally has amelting point of less than 100° C. and preferably a melting point in therange from 0 to 40° C. This is also true for the mixtures.

One of the preferred hydrophobic viscosity-increasing agents is ahydrophobicized nanoscale fumed silica. It increases the viscosity ofthe nonpolar organic compound(s) to the extent that they can beemulsified in the cellulosic shaping and spinning solution. Furthersuitable thickeners are polymers with olefinic and aromatic moieties,such as, for example, styrene-butadiene block polymers or short-chainpolyethylene types or phosphorus-containing esters. These are primarilybicyclic phosphorus-containing esters which additionally offer flameretardancy. Hydrophobicized, nanoscale sheet-like and/or elongatedparticles can also be used as thickeners. Surprisingly, a fraction ofthickeners of from 1 to 50% by weight, preferably from 5 to 20% byweight, based on the weight of the cellulose, suffices to bridge themuch greater differences in density and viscosity of an emulsion ofhydrocarbons in a cellulosic shaping and spinning solution, compared tohydrocarbon-in-water emulsions. The nanoscale fumed silica generallyconsists of particles with an average diameter from 30 to 200 nm,preferably from 40 to 100 nm.

Hydrophobicized, nanoscale, fumed silicas suitable for the processaccording to the invention are known. In the prior art, they serve forthe thickening of solutions (EP 0 745 372) and also the stabilization ofwater-in-oil or oil-in-water emulsions against separation of thedisperse phase by positioning the fumed silica at the oil/waterinterface (DE 10 2004 014 704). They can be used for “controlledrelease” systems.

The nanoscale, sheet-like, hydrophobicized particles are generallylikewise used in a fraction of from 1 to 50% by weight, preferably from2 to 20% by weight, particularly preferably from 5 to 12% by weight, ineach case based on the weight of the cellulose. These are preferablymodified sheet silicates, e.g. hydro-phobicized bentonite. The particlesgenerally have a length and width of about 200 to 1000 nm and athickness of about 1 to 4 nm. The ratio of length and width to thickness(aspect ratio) is preferably about 150 to 1000, preferably from 200 to500. Hydrophobicized elongated nanoscale particles can likewise be used,for example carbon nanotubes or carbon nanofilaments. Nanotubesgenerally have a diameter <1 to 30 nm, nanofilaments of ca. 150-300 nm.The length is up to several millimeters.

The nanoscale particles surround the organic material microphases with alayer of nanodisperse structures. The particles have the surprisingproperty that they stabilize the emulsion during shaping and then act asphase promoters between cellulose matrix and enclosed nonpolar organiccompounds.

In connection with the present invention, “nanoscale” is used to referto objects which have, in at least one dimension, a size from 1 to 100nm, as explained in the industrial standard ISO/TS 27687.

The enclosed nonpolar organic compounds can also be laden with activeingredients. These are nonpolar active ingredients which form solutionsor suspensions with the nonpolar organic compounds. The activeingredients are preferably plant products, such as jojoba oil, manoioil, evening primrose oil, avocado oil, cocoa butter, ethereal plantextracts or nonpolar plant extracts, fat-soluble vitamins, such asvitamin A, D and E, or insecticides, such as pyrethroids, specificallypermethrin, or repellents. The concentration of active ingredient(s) canbe from 0.001 g per kg up to 500 g and more, preferably from 50 to 150 gper kg of shaped article. The active ingredients can be released intothe surrounding area in a controlled manner over a prolonged period.This effect can be demonstrated e.g. using the washing permanency of thefunctional fibers.

The hydrophobicized nanoscale particles within the cellulosic shapedarticle can likewise be laden with nonpolar and other organic orinorganic substances. Such organic or inorganic substances include, forexample, dyes, pigments, flame retardants, Plasticizers, luminescentsubstances, UV absorbers, electrically or magnetically conductivesubstances, matting agents, fragrances, antibacterial activeingredients, fungicides and other functional additives. As a result ofweak intermolecular interactions, these molecules are reversiblyadsorbed. It is found that excess nanoscale particles preferentiallybecome concentrated at the surface of the shaped article and/or in thevicinity of the surface of the inclusions. This opens up a furtheroption of imparting additional functional properties to the shapedarticle. As a result of the ability of the cellulose to swell, theshaped articles can also be laden with nonpolar and weakly polarmaterials after the manufacturing process by nonpolar and weakly polarmaterials migrating from an aqueous phase to the surface of thenanoparticles, where they are reversibly adsorptively bonded. Thisprocedure is particularly well suited for substances which develop theireffect via the gas phase, such as repellents against insects, fragrancesof all types or medicinal active substances. Further additives in theshaped bodies may be: dyes, UV stabilizers, bactericidal substances,flame retardants, antistats, crosslinking agents, plasticizers,catalysts.

As the result of adding nonpolar organic compounds and mixtures in aconcentration of less than 200% (w/w), based on the weight of thecellulose dissolved in the spinning solution, the shaped articlescomprise less than 66% (w/w) of nonpolar organic substances or mixtures.

The process according to the invention leads to cellulosic shapedarticles which, compared to unmodified cellulose fibers, have asignificantly increased storage capacity for heat and/or nonpolar activesubstances, and the effect of which can be combined with furtherfunctionalities.

Additionally, the melting point of the phase change materials can belowered by mixing with other organic compounds and thus be adjusted tothe value desired in each case. The nonpolar organic compound(s) arealso suitable as solvents and/or storage medium for nonpolar organicactive ingredients. The active ingredients can be released in acontrolled manner from the inclusions in the cellulosic shaped articles.It is also possible to utilize the reverse effect, where the fibers withthe inclusions of nonpolar organic substances absorb gaseous and/orliquid nonpolar compounds (harmful substances).

The functional effect is based on the physical effect of heat storageand/or on the uniform and finely doseable storage and release ofnonpolar active ingredients, plant extracts and the like from the insideof the fiber. Through appropriate selection of the nonpolar fraction, itis also possible to produce by this process fibers which can serve asabsorption medium for liquid or gaseous, nonpolar substances. Furtherfunctional modes of action can be achieved through the selection ofspecific functional thickeners and/or sheet-like nanoscale additives,laden with functional active ingredients.

Using this process it is possible to produce cellulosic shaped articleshaving the effects already described, such as increased heat storagecapacity and “controlled release” functions, much more efficiently andcost-effectively since bulk materials can be processed and conventionalencapsulation and incorporation of micro-capsules is dispensed with. Theprocess according to the invention is variable. Thus, e.g. it ispossible to utilize the lowering of the melting point of mixtures inorder to adapt an industrial standard phase change material exactly to apregiven application temperature and/or to expand themelting/solidification range.

The shaped articles according to the invention can be processed,especially in the form of fibers, to give textiles which are used in theclothing industry, as industrial textiles and in the leisure sector.Specifically, the shaped articles provided with nonpolar activeingredients can also be used for medicinal or cosmetic purposes. Theshaped articles can also serve for producing special papers or filmswhich are laden with active ingredients.

The cellulosic shaped articles according to the invention have acellulose matrix and inclusions dispersed therein, where the inclusionscomprise one or more nonpolar organic compounds stabilized with ahydrophobic thickener.

The nonpolar organic compounds are preferably selected from the groupcomprising hydrocarbons, waxes, beeswaxes, oils, fatty acids, fatty acidesters, stearic anhydrides and long-chain alcohols, which in each casehave a melting point of less than 100° C. The fraction of the nonpolarorganic compounds is more than 10% by weight, preferably more than 30%by weight, and particularly preferably more than 40% by weight, based onthe weight of the cellulose.

One of the hydrophobic thickeners consists of nanoscale particles,preferably of hydrophobicized nanoscale fumed silica, and is present inan amount of from 1 to 50% by weight, based on the weight of thecellulose.

Moreover, the inclusions can comprise one or more active ingredientsfrom the group comprising plant products, jojoba oil, manoi oil, eveningprimrose oil, avocado oil, cocoa butter, ethereal plant extracts,nonpolar plant extracts, fat-soluble vitamins, vitamin A, D and E,insecticides, pyrethroids, permethrin and repellents. The activeingredients are present in an amount of up to 50% by weight, based onthe weight of the cellulosic shaped article.

In one particular embodiment, the cellulosic shaped article comprises abarrier material made of nanoscale layered particles and/or nanoscaleelongated particles, by means of which the nonpolar organic compoundsare retained in the inclusions and active ingredients are released in acontrolled manner. The fraction of the barrier material is 1 to 50% byweight, based on the weight of the cellulose.

In further embodiments, the cellulosic shaped article has, in atemperature range from 15 to 45° C., a specific latent heat of greaterthan 20 J/g, preferably of greater than 30 J/g and particularlypreferably of greater than 50 J/g.

The invention is illustrated in more detail below by reference to twodiagrammatic figures.

FIG. 1 shows a fiber 1 with cellulose matrix 2 and inclusions 3dispersed therein. The inclusions 3 comprise one or more nonpolarorganic compounds which are stabilized with at least one hydrophobicthickener.

Details of the inclusions 3 and of the cellulose matrix surrounding themare shown in FIG. 2 in a diagrammatic manner. A barrier material 4 ofnanoscale layered particles is dispersed in the cellulose matrix 2. Inparticular, the layered particles are present separately or exfoliatedin the cellulose matrix 2. Around the inclusions 3, the density of thebarrier material 4 is increased relative to its mean density in thecellulose matrix 2. Accordingly, the inclusions 3 are surrounded by azone of the barrier material, through which the nonpolar organiccompounds and optionally active ingredients present therein are onlyable to enter the cellulose matrix 2 via tortuous paths, if at all.Through suitable selection and dosage of the barrier material 4, thepermeability for active ingredients can be adjusted in a targeted manner(“controlled release system”).

The invention claimed is:
 1. A cellulosic extruded article comprising acellulose matrix and, dispersed therein, inclusions of nonpolar organiccompound(s), wherein said cellulosic extruded article comprises at leastone of (i) a viscosity-increasing hydrophobic agent, (ii) nanoscale,hydrophobicized sheet particles or (iii) elongated hydrophobicizedparticles, said sheet particles surrounding the inclusions as barriermaterial, the nonpolar organic compound(s) is present in an amount ofmore than 10% by weight, based on the weight of the cellulose matrix,and the hydrophobicized sheet particles are modified sheet silicates;wherein the barrier material consists of hydrophobicized bentonite; thenonpolar organic compound(s) have a melting point of less than 100° C.and is/are selected from the group consisting of hydrocarbons, waxes,beeswaxes, oils, fatty acids, fatty acid esters, stearic anhydrides andlong-chain alcohols, the hydrophobic viscosity increasing agent(s) ispresent in an amount of 1 to 50% by weight, based on the weight of thecellulose matrix, and said article has a specific latent heat of greaterthan 20 J/g in a temperature range from 15 to 45° C.
 2. A cellulosicextruded article comprising a cellulose matrix and, dispersed therein,inclusions of nonpolar organic compound(s), wherein said cellulosicextruded article comprises at least one of (i) a viscosity-increasinghydrophobic agent, (ii) nanoscale, hydrophobicized sheet particles or(iii) elongated hydrophobicized particles, said sheet particlessurrounding the inclusions as barrier material, the nonpolar organiccompound(s) is present in an amount of more than 10% by weight, based onthe weight of the cellulose matrix, and wherein the barrier materialconsists of hydrophobicized bentonite; active ingredients are present inan amount of up to 50% by weight, based on the weight of the cellulosicarticle, the hydrophobic viscosity increasing agent(s) is present in anamount of 1 to 50% by weight, based on the weight of the cellulosematrix, and said article has a specific latent heat of greater than 20J/g in a temperature range from 15 to 45° C.
 3. The cellulosic extrudedarticle as claimed in claim 1, wherein the nonpolar organic compound(s)have a melting point of less than 100° C. and is/are selected from thegroup consisting of hydrocarbons, waxes beeswaxes, oils, fatty acids,fatty acid esters, stearic anhydrides and long-chain alcohols.
 4. Acellulosic extruded article as claimed in claim 2 comprising a cellulosematrix and, dispersed therein, inclusions of nonpolar organiccompound(s), wherein said cellulosic extruded article comprises at leastone viscosity-increasing, hydrophobic agent and/or nanoscalehydrophobized sheet particles and/or elongated hydrophobicized particlesthat surround the inclusions as barrier material, wherein the nonpolarorganic compound(s) is a plant product active-ingredient and/or containsone or more active ingredients selected from the group consisting offat-soluble vitamins, insecticides and repellents, and said article hasa specific latent heat of greater than 20 J/g in a temperature rangefrom 15 to 45° C.
 5. The cellulosic extruded article as claimed in claim4, wherein the active ingredients are present in an amount of up to 50%by weight, based on the weight of the cellulosic article.
 6. Thecellulosic extruded article as claimed in claim 1, wherein thehydrophobic viscosity increasing agent(s) is present in an amount of 1to 50% by weight, based on the weight of the cellulose matrix.
 7. Thecellulosic extruded article as claimed in claim 1, wherein thehydrophobic viscosity-increasing agent consists of hydrophobicizednanoscale fumed silica.
 8. The cellulosic extruded article as claimed inclaim 1, wherein the barrier material is present in an amount rangingfrom 1 to 50% by weight, based on the weight of the cellulose.
 9. Thecellulosice extruded article as claimed in claim 1, wherein theinclusions are surrounded by a zone with increased density of thebarrier material.
 10. The cellulosic extruded article as claimed inclaim 1, wherein said article is a fiber and said fiber comprisesviscosity-increasing, hydrophobic agent and barrier material consistingof hydrophobicized bentonite sheet particles, said sheet particleshaving a length and width of about 200 to 1000 nm and a thickness of 1to 4 nm, and the fiber, according to a test in accordance with DIN EN26330 (1993), the loss of one or more nonpolar organic compounds after20 washes is less than 20% by weight, based on the amount of respectiveorganic compound originally present in the fiber.
 11. The cellulosicextruded article as claimed in claim 1, wherein said hydrophobicviscosity-increasing agent comprises phosphorus-containing esters and/orhydrophobicized nanoscale particles laden with flame retardantsimparting a flameproof finish.
 12. Textile sheet materials, papers orfilms comprising cellulosic articles as claimed in claim 1, wherein saidtextile sheet materials are optionally blended with other textile fibersand said papers or films optionally further comprise active ingredients.13. The cellulosic extruded article as claimed in claim 1, wherein thefraction of nonpolar organic compound(s) is more than 30% by weight,based on the weight of the cellulose matrix.
 14. The cellulosic extrudedarticle as claimed in claim 4, wherein the plant products are selectedfrom jojoba oil, manoi oil, evening primrose oil, avocado oil, cocoabutter, ethereal plant extracts, or nonpolar plant extracts, thefat-soluble vitamins are selected from vitamin A, D or E, and theinsecticides are pyrethroids.
 15. The cellulosic extruded article asclaimed in claim 1, wherein said article has a specific latent heat ofgreater than 50 J/g in a temperature range from 15 to 45° C.
 16. Thecellulosic extruded article as claimed in claim 1, wherein saidcellulosic extruded article comprises (i) said viscosity-increasingagent and (ii) said nanoscale sheet and/or elongated hydrophobicizedparticles.
 17. The cellulosic extruded article as claimed in claim 1,wherein tire nonpolar organic compound is selected from the groupconsisting of hydrocarbons, waxes, beeswaxes, oils, fatty acids, fattyacid esters, stearic anhydrides and long-chain alcohols and the fractionof nonpolar organic compound(s) is more than 40% by weight, based on theweight of the cellulose.
 18. The cellulosic extruded article as claimedin claim 1, wherein the cellulosic extruded article is a fiber, a paperor a film.
 19. The cellulosic extruded article as claimed in claim 18,wherein the cellulosic extruded article is a fiber and said fiberincludes at least one hydrophobic, viscosity-increasing agent asstabilizer and nanoscale, sheet-like and/or elongated, hydrophobicizedparticles as barrier material.
 20. A process for producing cellulosicshaped articles as claimed in claim 1 with inclusions of at least onenonpolar organic compound by the dry-wet extrusion process, said processcomprising preparing an emulsion with at least one nonpolar organiccompound in a solution of cellulose in a solvent and stabilizing saidemulsion by adding at least one hydrophobic viscosity-increasing agent,and/or adding nanoscale, sheet-like hydrophobicized bentonite and/orelongated, hydrophobicized particles to the emulsion that surrounddroplet-like inclusions of the nonpolar organic compound(s) and form asuspension, and recrystallizing the cellulose to produce shaped articleswith a cellulose matrix in which the nonpolar organic compound(s) is/areincorporated in disperse form.
 21. The process as claimed in claim 20,wherein the nanoscale particles are hydrophobic viscosity-increasingagents, the sheet-like, hydrophobicized particles are hydrophobicizedbentonites and the elongated particles are nanotubes or nanofilaments.22. The process as claimed in claim 20, wherein the hydrophobic agent isnanoscale structured, fumed silica or polymers with olefinic andaromatic moieties.
 23. The process as claimed in claim 20, wherein thesolvent is a tertiary amine oxide or an ionic liquid.
 24. The process asclaimed in claim 21, wherein the hydrophobic agents are present in anamount ranging from 1 to 50% by weight, based on the weight of thecellulose.
 25. The process as claimed in claim 21, wherein the modifiedsheet silicates are hydrophobicized bentonites.
 26. The process asclaimed in claim 20, wherein dyes, UV stabilizers, bactericidalsubstances, flame retardants, antistats, crosslinking agents,plasticizers and/or catalysts are added both to the hydrophobic agent(s)and also the sheet-like nanoparticles.